Apparatus for producing hydrogenated hydrocarbon products



May 18, 1943 R. LEPRESTRE P -rAL 2,319,508

' APPARATUS Fon Pnonucme HYDROGENATED HYDRocARBoN PRODUCTS original Filed May 1o, 1958 2 sheets-sheet 1.

Patented May 18, 1943 APPARATUS FOR PRODUCING HYDROGEN- ATED HYDROCARBON PRODUCTS Rene Leprestre, deceased, late of New York, N. Y.,

by Margaret Cornell Leprestre, Reading, Pa., H. Y Douglas Hadden, Westport, Conn., Ralph C. Tobin and Joseph Dannenberg, New York,

N. Y., executors Original application May 10, 1938, Serial No.

207,095. Divided and this application December 26, 1941, Serial No. 424,556

Claims.

This invention relates to an apparatus lfor producing hydrogenated hydrocarbon products, for example, motor fuel of high octane value and this application is a division of application, Serial No, 207,095, filed May 1D, 1938, now Patent No. 2,271,017, dated January 27, 1942, on a method of making such products. Y

While the apparatus of the present invention is susceptible of use for other processes in the manufacture of hydrogenated hydrocarbon products, it is specially designed to provide a novel means for controlling the involved process in such a manner as to obtain hydrocarbons of different hydrogen content, as well as to provide novel means for pre-heating the hydrocarbon mixture and the hydrogen or hydrogen carrier before they are injected into the retort of the reaction chamber.

Also, a further object of the invention is to provide simple and expeditious means for renewing the catalytic element when its eiciency has been reduced by continued operation, and other objects of the invention will more readily appear, as the nature of the same is better understood, the same consisting in the novel apparatus hereinafter more fully set. forth and claimed..

A preferred form of the apparatus is shown in the accompanying drawings, in which:

Figure 1 is a vertical sectional View of the retort.

VFigure 1a is a diagrammatic side elevation of the complete retort.

Figure 2 is an enlarged detail sectional view of the upper portion of the retort. i

Figure 3 is an enlarged vertical sectional view of the bottom of the retort. Y

Figure 4 is a diagrammatic view of the preferred arrangement of nozzles for the hydrogen and the colloidal solution.

In carrying outthe invention, the rst step is to prepare 'an aqueous mixture of the hydrocarbon base material -to be hydrogenated, and to incorporate in the mixture a small percentage of a suitable emulsion stabilizer, such, for instance, alcohol.

The hydrocarbon, water and alcohol are emulsified in suitable colloid mills to` reduce the entire mass completely to its colloidal state;A This vcolloidal emulsion is then heated under pres'- sure to approximately 1000 to 1200 F, and

pumped under high pressure, according to the material to be treated, into the reactionA chamber through opposed nozzles so directed that the jets impinge upon eachother. The chamber pres- `pinging chamber M as will later appear.

sure will be that required for the conversion of the particular mixture into the desired hydrocarbon fraction and the pump pressure must be sufciently higher than this to insure sufficient jet velocity to break the mixture up into line spray. Water gas Vor hydrogen is also injected into the chambers through another pair of opposed nozzles set in the same plane as the mixture nozzles and so set that the jets impinge both on each other and on the points of impact of the mixture jets. The pressure of the hydrogen is determined by the same considerations as those determining the pressure of the mixture. Both the mixture and the hydrogen reach the nozzles through pipe vcoils contained in the upper end of the retort through which means the entering mixtures are preheated toany desired degree, according to the material'to be treated, less than the retort temperatures, and simultaneously the exit gases from the retort are cooled.

The mixture of spray and gas from the nozzles passes upwardly through the retort and is thus carried through the catalytic material and, due to the combinations of pressure, temperatureand action of the catalyst, the chemical reactions are completed to produce hydrocarbon fractions of the desired composition.

Preparatory to starting the retort, it is brought up to the desired temperature by the use of the heating coil in the lower section of the retort. AAfter the reactions have started, any added heat `observed that the retort includes a suitable column or casingA I provided at its upper en d with the flange portion 2 for facilitating the securing of a cap or cover structure C thereto by the use of suitable bolts 3, while the bottom of the column is provided with the flange v#which provides adequate means for anchoring a` base plate 5 thereto by the bolts 6 or equivalent fastenings.

The lower/portion of the casing I is lined with suitable refractory` material 'lsurrounding an electrical heating' element inthe form of an annular member 8 which provides a mixing or im- The heating element 8 has the electrical wires 9 coiled about its outer face so that the inner face thereof presents a smooth unbrokensurface. The electrical connections for the heating Wires 9 may be madethrough the conduit lla (Fig. 3) in the base plate 5.v The lower portion of the heating element 8 is embedded in the horizontal layer of refractory material I covering the inner face of the-base 5, and, at this point, it may be noted that the said base is suitably constructed to provide for the insertion of one or more pyrometers P and P' and a pressure gauge G.

The cap structure C carries therewith suitable pipes I2 and for supplying the hydrogen and the mixture or colloid t0 the retort, and also carries the catalytic unit A so that when the bolts 3 have been disconnected from the flange 2, the entire cap structure C and its associated parts may be lifted bodily out of the retort by the use of a crane or other suitable lifting apparatus. In that connection, it will, of course, be understood that the pipes and I2 which respectively supply the mixture or colloid and the hydrogen are provided with suitable joints which may be disconnected when it is desired to lift the cover C from the retort of the casing I.

The catalyst A (for example), iron oxide, is contained in a basket I3 having a foraminous bottom wall I3ab engaged and supported by the head I4 of a rod I5 when the cover structure C is removed from the casing. In that connection, however, it will be observed that the said bottom wall |37a of the basket may rest upon the annular abutment 8a of the heating element when the basket is in use as shown in Figure 1. That is to say, the upper end of the rod I5 extends through a strap or bracket I6 carried by the cover structure and the nut II on the rod is preferably so positioned that the cover will have a certain amount of play relative to the rod, thus insuring the proper degree of tolerance to permit the basket to rest on the annular abutment 8a, of the heating element, and at the same time permit the cover structure including the plate C', to ilushly seat on the flange 2. The foraminous basket which holds the catalyzer A is surrounded by refractory blocks I3b which may have lateral expansion passages therebetween.

Referring further to the cap or cover structure C, it is pointed out that the mixture pipe I I carried by the cover is formed internally of the retort, that is, Within what may be termed a gas collecting chamber, or a preheating chamber N, with a mixture preheating -coil IIa, and likewise, the portion of the hydrogen pipe I2 at the underside of the cover C is formed into a hydrogen preheating coil I2a so that both the mixture pipe and the hydrogen pipe are coiled within the upper portion of the retort labove the catalyzer unit A. The lower end ||b ofthe mixture pipe extends through the catalyzing material A in the basket I3 and projects into the mixing chamber M where it is provided with the horizontal branchpipe ||c which is preferably of arcuate formation (Fig. 4) and provided with diametrically disposed nozzle portions I I@l forming jets disposed in opposed relation toward the axis of the mixing chamber M so that high pressure streams of mixture issuing from opposite jets impinge upon each other, in the mixing chamber, while the device is in operation.

Similarly, the lower portion of the hydrogen pipe below the coil I2a is provided with an extension I2b which passes through the catalyzing material A in the basket I3 and thence through the bottom of the basket into the mixing chamber where it is also provided with an arcuate branch pipe I2c formed with diametrically disposed hydrogen discharging nozzles I 2d. These nozzles are preferably arranged in the same plane as the nozzles ||d and are located at an angle of 90 to said mixture discharging nozzles. The effect of arranging the nozzles I Id and I2cl in the manner shown in Figure 4, for example, is to provide oppositely discharging jets of mixture and hydrogen which impinge on each other at the axis of the mixing chamber at the same time, and because of the high pressure at which the mixture and hydrogen are discharged against each other they are thoroughly mixed or broken up at their point of contact. This mixture forces itself through the catalyzing chamber upwardly into the chamber N at the upper end of the rctort, said chamber containing the preheating coils I I@ and |2a, respectively for the colloid mixture and the hydrogen.

When the gases reach the top of the chamber N they have given up considerable heat to the coils IIa and I2, and therefore they are considerably lowered in temperature as compared with the heat in the mixing chamber.

From the chamber N the products pass through a valve orifice Whose area may be accurately controlled and predetermined to permit obtaining different qualities of hydrocarbon distillate. That is to say, if it is desired to produce, for example, high octane gasoline, the valve orifice is set to produce a very small or limited clearance which has the effect of keeping all of the mixture in the retort longer, thus subjecting them to prolonged contact with the catalyzer to insure more thorough union of the hydrogen and hydrocarbon vapors. On the other hand, if it is intended to produce low octane hydrocarbon products the valve orifice may be opened wider or, in other words, a greater outlet area or clearance may be provided which will allow the products to escape quicker from the retort and hence with a shorter period of Contact with the catalyzer.

Referring to Figure 2 it will be apparent that the gases in the chamber N are permitted to pass therefrom to the condenser (not shown) through the valve orifice I8 which operates in conjunction with a valve head I9 formed at one end of hollow stem 2. This stem has external threads 2| so that when it is turned or rotated by the hand Wheel 22, the position of the valve head I9 may be varied relative to the seat I8. As the products pass between the valve seat I8 and the head I9 it enters a chamber 23 in the cover, the said chamber being connected to an outlet tube 24 leading to a condenser, The hollow stem of the valve assembly is provided with a water inlet pipe 25 whose discharge end extends in close Aproximity to the valve head I9, and a water take-off connection 26 is provided for the hollow stem 20 above the hand wheel. Also, it will be seen that a suitable packing 21 is provided about the hollow valve stem 20 above the chamber 23 and below the screw threads 2|. However, to fully utilize any gas that may escape past the packing 21, there is provided above said packing a trap chamber 28 which in turn is provided with a take-oil' 29 leading to the condenser. The packing 21 is preferably in the form of a spool thus enabling a water jacket to be formed about the medial portion of the valve stem 20,'the said jacket being provided with a water inlet connec` tion 30 and a water outlet 3|. In addition, the face of the cover C exposed to the gases within the chamber N may be provided with a water jacket 32, suitable inlet and outlet connections being provided for the purpose.

.The upper outerportion of the column in the zone of the chamber N may also be provided with a water jacket 33. the said jacket being provided with a water inlet connection Stand an` outlet connection 35. f. Y Referring to the general operation of the apparatus andthe several stages of the process `per,-

formed therein, it is pointed out thatt-he hydrocarbon base material, in finely divided or colloidal form, is pumped -orintroduced into the retort throughthe supply connection` II. The hydro,- carbon mixture then proceeds through the pre- ,heating coil IIa, and thus becomes heated as it flows downwardly toward the mixingchamber` M through the pipe .extension II! `When the preheated hydrocarbon mixture reaches the branch pipe I I, it is forced through opposed branch nozzles I I1 thus forming opposing mixture. jets which impinge upon each other with great force at approximately the axis of the mixing chamber M. l

, Simultaneously, with the introduction ofthe hydrocarbonmixture into the retort, hydrogeny gas-enters the pipe I2 and then passesthrough the preheating. coil. I2,i and pipe section |21. to the branchconnection I2c whereupon the hydrogen, is 1 discharged through the opposed nozzles I2d, in jet form,not `only to causethehydrogen jets to impingeupon themselves butto also impinge uponthe hydrocarbon mixture jets discharging from the nozzles IId.

According to one example, the ,hydrocarbon mixture and hydrogen 4mayboth-,beforced into the nozzles at approximately 12,000 4to 14,000 pounds pressure.

The chamber M, as previously indicated is preheated before the hydrogen and hydrocarbon mixture are introduced and is subsequently maintained at the required temperature, for example, approximately 1000 F., in the example now given, by the electric heating element 9. Thus, when the hydrogen and the hydrocarbon mixture are pumped into the mixing chamber Vat a uniform 'pressure as above indicated the resultant mixture is forced upwardly through the bed of catalyst in the basket I3.

After the mixture is transformed into new products by the catalyst it passes through the chamber N, which, as previously explained, is entirely closed except for the valve I8-I9 which is definitely and accurately set at a predetermined clearance. If the valve is so adjusted as to hold back the gases in the chamber N, or in other words, if the valve is set with only a comparatively small opening, it will be apparent that the gases are held for a prolonged period of contact near the wall thereof so thatthe temperature can be' maintained at the desired degree under all conditions` of use. Moreover, through .the `medium of .the pressure gage Gthe pressure in the relief valve of any approved type may be. placed with the catalyst to produce a motor fuel having Taking one example, as an illustration, if it is desired to produce a lower grade gasoline (68 to 'Z0 octane) it is necessary to open the valve wider, and also change the pressure and the quantity of hydrogen. In this example, the pressure of hydrogen and hydrocarbon mixture may be lowered to from 5000 to 8000 pounds, and the temperature maintained in the mixing 'chamber at approximately l000 F. While the process has been operated at temperatures from approximately 900 F. to 1150 F, it is obvious to those skilled in the art that varying both temperature and, or, pressure will result in the formation of different hydrocarbons. It is likewise obvious that the high limits are governed by the construction of the reaction chamber.

The mixing and impinging chamber M may be accurately checked as to temperature through the medium of pyronieters` P and P' located substantially at the axis of the mixing chamber and The productsof Athe reactions occurring inthe catalyst chambermay be released .to atmospheric pressure 'by the` controlyalve I 8-I9 and the vapor ,mixture thus produced Cooled and` con,- densed by conventional-means and anyresidual gases subsequentlyseparated. `It will be understood, :hoy/ever, thatcooling and condensation of the .products may` be carried out under pressure, if desired; such ,pressures -would ordinarily be belowy the` operatingpressures of the :catalyst chamber. Condensation of the `products under moderate pressures has the advantage of ,retaining very volatile hydrocarbonsinthe condensate. However, the means employed Afor, Acondensation of motor fuels and the like are well .understood in the -art and are not a part of thisinvention;

VFrom the foregoing it -willM-be Lapparentthat the distinctive features. ofthe presentinvention reside in the provision of a heated mixing chamber into which hydrocarbon mixture and hydrogen may be injected and mixed in the presence of controlled heat, pressure, and water gas, thereby to produce a new mixture. This mixture forces its way through the catalyst containing basket I3 which brings about the complete union of the constituents and forms new reaction products.

Inasmuch as the colloid and water gas supply pipes, and their coils, are carried by the cover, and the catalyzer basket I3 is also connected to the cover, it will be apparent that the entire interior assembly of the retort may be removed when desired, or when the catalyzer requires removal.

From the foregoing itis thought that the construction, operation and many advantages of the herein described apparatus will be understood without further description, and also that changes in the form and minor details of construction may be resorted to without departing from the spirit of the invention as covered by the appended claims.

It is claimed:

1. An apparatus for hydrogenating hydrocarbons comprising a retort column having a mixing chamber at its lower end and a gas collecting chamber at its upper end, valve means for controlling the flow of gases from said collecting chamber, heating means for the mixing chamber, a foraminous basket containing a catalyzer and arranged between the mixing chamber and the collecting chamber, and means for introducing hydrogen and an aqueous colloidal mixture of a hydrocarbon into the mixing chamber, said means comprising a plurality of hydrogen jets and a plurality of solution jets arranged substantially in the same horizontal plane and disposed at an angular relation of 2. An apparatus for increasing the hydrogen content of hydrocarbons comprising a retort column, a cover and a base removably fitted to said column,A anl annular heatingA element arranged at theA bottomv of the column andproviding a mixing chamber, hydrogen and colloidal solution supplying pipes each including coilportions carried' by the cover and having extensions-provided with nozzles positioned' in said mixing chamber, and a foraminous basket also` carried by the cover for holding catalyzing material, said foraminous basket having a slidable connection-with the cover whereby the latter may be fitted onv the topof the column when the basket is appliedv to the top of the mixing4 chamber.

3; An apparatus for increasing the hydrogen content of hydrocarbons comprising a retort col-v umn having a cover and a base removably fitted thereto, an annular` member surrounded by a heating coil supported by the base and forming a mixing chamber, a-.pyrometer and a pressure gage disposedinvsaid-mixing chamber, a catalyzer unit above the said annular member, hydrogen gas supply means andi colloidal solution supply means both carried` by the cover and each having a coiled' portion disposed Within thev column above said mixing chamber and alsohaving nozzleslo'- cated in said mixing chamber, and valve means carried by the cover for controlling the passage of gas from said retort.

4. An apparatus for increasing the hydrogen contentof hydrocarbon products comprising a retort column provided with a gas collecting chamber within its upper end, valve means for controlling the outlet of gases from said collectingV chamber, an annular heating element arranged within the lower portion of the column and providing a mixing chamber, a catalyzer unit arranged Within the retort column between the upper'collecting chamber and the lower mixing chamber and in communication with both of said chambers, andv hydrogen-carrier and colloidal solution supply pipes each extending through the upper collecting chamber and provided withdischarge nozzles disposed Within said mixingv chamber.

5. Anr apparatus for increasing the hydrogen content of hydrocarbon products comprising a retort column provided. with alr gas. collecting chamber Within itsv upper end', valve means for controlling the outlet of. gases from said collecting chamber, an annular heating element arranged within the bottom portion4 of the column and providing a mixing chamber, alcatalyzer unit arranged within the retort column betweeny the upper collecting chamber and the lower mixing chamber and in communication with both of said chambers, and hydrogen-carrier and colloidal solution supplyA pipes ea'ch having pre-heating coils within said collecting chambers and each provided with discharge nozzles disposed within said mixing chamber.

MARGARET CORNELL LEPRES'IRE. H` DOUGLAS HADDEN. RALPH C. TOBIN. JOSEPH DANNENBERG. Eecuto'rs of the Estate of ReneY Leprestre,

Deceased. 

